EP0541174A1 - Compositions contenant du polyalkylène à faible poids moléculaire et de copolymère séquencé hydrogéné de poly(vinylaromatique/diène conjugué) et leur applications nouvelles - Google Patents

Compositions contenant du polyalkylène à faible poids moléculaire et de copolymère séquencé hydrogéné de poly(vinylaromatique/diène conjugué) et leur applications nouvelles Download PDF

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Publication number
EP0541174A1
EP0541174A1 EP92203380A EP92203380A EP0541174A1 EP 0541174 A1 EP0541174 A1 EP 0541174A1 EP 92203380 A EP92203380 A EP 92203380A EP 92203380 A EP92203380 A EP 92203380A EP 0541174 A1 EP0541174 A1 EP 0541174A1
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Prior art keywords
block copolymer
parts
weight
poly
amount
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German (de)
English (en)
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Hans Ferdinand Vermeire
Hans Roger Henri Dendooven
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Shell Internationale Research Maatschappij BV
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Shell Internationale Research Maatschappij BV
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L29/00Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical; Compositions of hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Compositions of derivatives of such polymers
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00Compositions of unspecified macromolecular compounds
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L53/00Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L53/02Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes
    • C08L53/025Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes modified
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04Homopolymers or copolymers of ethene
    • C08L23/06Polyethene
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/10Homopolymers or copolymers of propene
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/18Homopolymers or copolymers of hydrocarbons having four or more carbon atoms
    • C08L23/20Homopolymers or copolymers of hydrocarbons having four or more carbon atoms having four to nine carbon atoms
    • C08L23/22Copolymers of isobutene; Butyl rubber ; Homo- or copolymers of other iso-olefins
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L91/00Compositions of oils, fats or waxes; Compositions of derivatives thereof

Definitions

  • the invention is relating to low molecular weight poly(alkylene) and hydrogenated poly(vinyl aromatic/conjugated diene) block copolymer containing compositions and their novel applications.
  • low molecular weight poly(alkylene) in combination with hydrogenated poly(vinyl aromatic/conjugated diene) block copolymers and more in particular the use of low molecular weight poly(alkylene) in combination with poly(styrene/butadiene) or poly(styrene/isoprene) block copolymers, the elastomeric blocks of which have been selectively hydrogenated, was known for applications of said compositions as insulating filling gels, adhesives and sealants.
  • sealant compositions which comprised hydrogenated thermoplastic elastomer, a low molecular weight polyalkylene plasticizer, a modifying resin selected from the group consisting of modified and unmodified rosin and rosin esters, esters of polymerized rosin, polyterpene resins, terpene-phenolic resins, coumarone-indene resins, diolefin-olefin resins, phenol-aldehyde resins and aromatic resins, said resin being present in an amount within the range of 10 to 300 parts by weight per 100 parts by weight of hydrogenated thermoplastic elastomer, and a filler selected from calcium carbonate, aluminium silicate, clay, talc, kaolin and silica, in an amount within the range of 25 to 250 parts per 100 parts by weight of said hydrogenated thermoplastic elastomer.
  • a modifying resin selected from the group consisting of modified and unmodified rosin and rosin esters, esters of polymerized rosin,
  • the plasticizer was indicated to be present preferably in an amount of 25 to 175 parts by weight per 100 parts by weight of said hydrogenated thermoplastic elastomer, and is preferably selected from homopolymers of ethylene, propylene, 1-butene, cis-2-butene, trans-2-butene, isobutylene, pentenes etc. as well as copolymers and terpolymers thereof in all proportions and mixtures thereof, said polymers possessing weight average molecular weights from 200 to about 3000 and preferably from 300 to 2000.
  • the US patent No. 4,176,240 disclosed a filling material, having improved handling characteristics and useful for waterproofing electrical cables and comprising a styrene-ethylene-butylene-styrene block copolymer dissolved in (white) mineral oil and polyethylene, the latter being added for consistency.
  • US patent No. 4,617,422 disclosed a fully-filled telecommunication cable comprising a plurality of metallic conductors each coated with cellular insulation and a sheath enclosing said conductors and containing a filling medium comprising (by weight):
  • a liquid polybutene with a number average molecular weight between 200 and 4000 or a low molecular hydrocarbon resin Preferably as said second component of the base is used a liquid polybutene with a number average molecular weight between 200 and 4000 or a low molecular hydrocarbon resin.
  • lines 24-28 there was taught that as the molecular weight of the polybutylene increases as compared with the specified range, the solubility and gel forming ability of the block copolymer is impaired and the resulting composition tends to become more tacky.
  • the plasticizing oil was selected from the group consisting of petroleum paraffinic oils, petroleum naphthenic oils, and mixture thereof.
  • plasticizing oil was selected from the group consisting of petroleum paraffinic oils, petroleum naphthenic oils, synthetic polybutene oils, synthetic polypropylene oils, synthetic polyterpene oils and mixtures thereof; said oils having an average molecular weight of between about 200 to about 700.
  • plasticizing oils applied in the indicated amounts led to bleeding out of unacceptable amounts of such plasticizing oils in compositions containing more triblock copolymer.
  • US patent No. 4,716,183 disclosed adhesive compositions comprising: about 2 to about 30 parts by weight of a mixture of poly(styrene-ethylene-butylene-styrene) triblock copolymers; and about 70 to about 98 parts by weight of a hydrocarbon oil; and wherein the mixture of triblock copolymers comprises:
  • the preferred oils should be mixtures of non-aromatic paraffinic/naphthenic hydrocarbon oils.
  • compositions which comprised 2-30% by weight of a hydrogenated poly(styrene-butadiene-styrene) triblock copolymer and 70-98% by weight of plasticizer to be used as cable sealing compositions.
  • the polystyrene block-poly(ethylene-butylene) block weight ratio was in the range of from 27-35 to 65-73.
  • the oils useful for said composition had a molecular weight in the range of about 400 to about 2500 and most preferably from about 450 to about 1500, and a solubility parameter in the range of about 6.0 to about 8.5 and preferably in the range from 6.5 to 7.8.
  • Preferred oils included paraffinic and/or naphthenic oils, synthetic polyalpha-olefin oils, polypropylene oils and polybutene oils.
  • solubility parameter of the oil will decrease with an increase in molecular weight and in case of paraffinic/naphthenic oils, the solubility parameter decreases for increasing paraffin content.
  • Component (C) is preferably i.a. low molecular weight polyethylene, low molecular weight polypropylene and the like.
  • thermoplastic elastomer compositions for sealing material in water cisterns were known, which were comprising:
  • the composition did not exhibit excretion or migration of plasticizers.
  • compositions which comprise:
  • the block copolymers to be used as component (a) are preferably linear or star shaped block copolymers, which have been derived from a living block copolymer, having at least one block derived from predominantly a vinyl aromatic compound and preferably styrene and at least one block derived from predominantly conjugated diene, and obtained by means of anionic polymerization, optionally by coupling with a suitable polyfunctional coupling agent and subsequent selective hydrogenation of the poly(conjugated diene) blocks, and bearing terminal poly(vinyl aromatic) blocks in a sufficient degree in order to provide characteristic thermoplastic elastomer properties.
  • component (a) also mixtures of triblock or star shaped block copolymers and the terminated preceding starting diblock copolymer can be used or diblock copolymers alone.
  • More preferred block copolymers have the structure SBS, SIS, (SB) n X or (SI) n X wherein S represents a block derived from styrene, ⁇ -methylstyrene, 4-n-propylstyrene, 3-methylstyrene, 1-vinylnaphthalene, 2-vinylnaphthalene and the like, of which styrene being preferred, and B represents a block derived from 1,3-butadiene; isoprene; 2,4-hexadiene; 3-ethyl-1,3-pentadiene and the like, of which 1,3-butadiene and isoprene are preferred.
  • the polymer blocks B have an apparent molecular weight of from 25,000 to 200,000 and the poly(styrene) block-poly(ethylene-butylene) block weight ratio is in the range of from 27-35 to 65-73. More preferably the copolymer blocks A have apparent molecular weights from 7500 to 50,000, while the polymer blocks B have apparent molecular weights from 30,000 to 150,000.
  • block polymer grades identified as KRATON G-1650, KRATON G-165X (KRATON-RP-6904), KRATON G-1651 and KRATON G-1652 or combinations thereof are used.
  • the density may range from 0.902 to 0.910 g/cc at 22.8 °C, while the flex modulus may range from 8780 to 17,580 g/cm2.
  • the preferred poly(vinyl aromatic) is polystyrene.
  • the notations " M ⁇ w " and “ M ⁇ n " are generally used for respectively the weight average molecular weight and the number average molecular weight.
  • a preferred group of flow promoting resins, embraced by component (c) of the composition, if any, consists of low molecular weight hydrocarbon resins, particularly those, said to be derived largely from alpha-methylstyrene, sold by Hercules Powder Company under the trade name Kristalex (Kristalex is a Trade Mark) and having ring and ball softening points (ASTM-E28) between 20 and 140 °C and more particularly between 60 and 120 °C.
  • additives can be added to the present composition e.g. antioxidant, e.g. Irganox (Irganox is a Trade Mark) and/or stabilizers against UV light and actinic light (e.g. Tinuvin (Tinuvin is a Trade Mark)), usually in amounts less than 2 parts by weight per hundred parts by weight of block copolymer, whereas as other additives can be used dyes, flame retarders and the like, in amounts of from 0 to 50 phr for each additive.
  • antioxidant e.g. Irganox (Irganox is a Trade Mark) and/or stabilizers against UV light and actinic light (e.g. Tinuvin (Tinuvin is a Trade Mark)
  • Tinuvin Tinuvin
  • other additives can be used dyes, flame retarders and the like, in amounts of from 0 to 50 phr for each additive.
  • An important advantage of the present compositions is the enablement of the novel applications of hydrogenated block copolymers, which seemed impossible or hardly acceptable up to now, such as elastic film, medical, wire and cable enrobing, automotive, flooring and roofing applications, and application in sporting goods, such as grips for golfclubs, tennis rackets and fishing rods.
  • compositions of the present invention can be prepared by a process, comprising the following steps:
  • Another aspect of the present invention is formed by the use of the hereinbefore specified compositions and by shaped articles obtained from these compositions.
  • a preblend of 100 parts by weight of KRATON G-1650, 50 parts by weight of polypropylene (PP SM 6100), 20 parts by weight of flow promoting resin (Kristalex F 120), 0.2 parts by weight of antioxidant (Irganox 1010) and 0.5 parts by weight of DLTDP (Irganox PS 800) was prepared using a Papenmeier mixer for 20 minutes at room temperature and the obtained mass was subsequently mixed in a Berstorff (Berstorff is a Trade Mark) 25 mm co-rotating twin screw extruder, having a screw speed of 280 rpm. The extrudate was cooled in a water bath and granulated through a Reeves (Reeves is a Trade Mark) granulator.
  • Reeves is a Trade Mark
  • the sheet was cooled to room temperature and subsequently granulated through a Sagitta dicer (Sagitta is a Trade Mark).
  • the obtained composition was injection moulded into 150 x 150 x 2 mm test plates using a Demag D 150 injection moulder.
  • the mould cavity was fan-gated over one side to give a well defined flow pattern during moulding.
  • the injection moulded plates were then conditioned for at least 16 hours in standard atmosphere, T: 23 °C, humidity: 50%, before testing.
  • compositions were prepared starting from the components, as specified in Table A.
  • Witco 260 (Witco is a Trade Mark) was used as the oil plasticizer in Comparative Formulations (A), (B) and (C).
  • Type (C) dumbbells according to ASTM D412, were cut from the conditioned injection moulded plates. These plates were used to measure the stress/strain properties: moduli, tensile strength, elongation at break, tensile set and set at break. The distance between the bench markers on the dumbbells was 25 mm. Crosshead speed of the Zwick Mechanical Tester was 500 mm/min, except for measuring tensile set for which the crosshead speed is set according to ASTM D412. The results are given in Table B.
  • the indentation Shore A hardness was measured according to ASTM D2240 with a Durometer on a stack of three 2 mm thick samples after 0 s (initial indentation) and after 30 s. The results are given in Table B.
  • MFR M elt F low R ate
  • the results in Figure 1 show the change in weight and the results in Figure 2 show the change of linear shrinkage of the circular test pieces during hot air ageing.
  • Injection moulded plates from the selected formulations were also aged under conditions as described above. Every four weeks, type (C) dumbbells and angle tear test pieces as mentioned above, were cut from these plates, and used to measure physical properties. Hardness Shore A was measured according to ASTM D2240 on a stack of three 2 mm thick injection moulded samples after 0 s (initial indentation) and after 30 s. The results are shown in Tables C and D.
  • compositions were prepared starting from the components as specified in Table E. Apart from the plasticizer (Hyvis 200), the preblend contained all the specified compounding ingredients.
  • compositions were prepared starting from the components as specified in Table G. Apart from the plasticizer (Hyvis 200), the preblend contained all the specified compounding ingredients.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)
EP92203380A 1991-11-04 1992-11-02 Compositions contenant du polyalkylène à faible poids moléculaire et de copolymère séquencé hydrogéné de poly(vinylaromatique/diène conjugué) et leur applications nouvelles Withdrawn EP0541174A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP91202860 1991-11-04
EP91202860 1991-11-04

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EP0541174A1 true EP0541174A1 (fr) 1993-05-12

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Country Status (8)

Country Link
US (1) US5278220A (fr)
EP (1) EP0541174A1 (fr)
JP (1) JPH05214208A (fr)
KR (1) KR930010107A (fr)
AU (1) AU661055B2 (fr)
BR (1) BR9204220A (fr)
CA (1) CA2081922A1 (fr)
TW (1) TW209877B (fr)

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WO1995003447A1 (fr) * 1993-07-23 1995-02-02 Shell Internationale Research Maatschappij B.V. Support pour tapis derive de compositions de copolymeres sequences
WO1995017467A1 (fr) * 1993-12-20 1995-06-29 H.B. Fuller Licensing & Financing, Inc. Materiau translucide comme le verre
WO1996015189A1 (fr) * 1994-11-15 1996-05-23 The Dow Chemical Company Couches provenant de dispersions aqueuses de copolymeres en blocs contenant un bloc diene conjugue hydrogene
US5578674A (en) * 1993-01-08 1996-11-26 The Dow Chemical Company High-strength films of block copolymer latices
US5905097A (en) * 1993-01-08 1999-05-18 The Dow Chemical Company High-strength breathable films of block copolymer lattices
US7718721B2 (en) 2006-11-13 2010-05-18 Sabic Innovative Plastics Ip B.V. Poly(arylene ether)/polyolefin composition, method, and article
WO2018172148A1 (fr) 2017-03-22 2018-09-27 Ineos Styrolution Group Gmbh Mélange de copolymères styréniques à faible retrait

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US7022765B2 (en) * 2004-01-09 2006-04-04 General Electric Method for the preparation of a poly(arylene ether)-polyolefin composition, and composition prepared thereby
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US8389615B2 (en) * 2004-12-17 2013-03-05 Exxonmobil Chemical Patents Inc. Elastomeric compositions comprising vinylaromatic block copolymer, polypropylene, plastomer, and low molecular weight polyolefin
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US5578674A (en) * 1993-01-08 1996-11-26 The Dow Chemical Company High-strength films of block copolymer latices
US5905097A (en) * 1993-01-08 1999-05-18 The Dow Chemical Company High-strength breathable films of block copolymer lattices
EP0618261A1 (fr) * 1993-04-02 1994-10-05 Shell Internationale Researchmaatschappij B.V. Bandes transporteuses dérivés de compositions thermofusibles à base de copolymères blocs hydrogénés dérivés d'un monomère vinyl aromatique et d'un diène conjugué
WO1995003447A1 (fr) * 1993-07-23 1995-02-02 Shell Internationale Research Maatschappij B.V. Support pour tapis derive de compositions de copolymeres sequences
AU686655B2 (en) * 1993-07-23 1998-02-12 Shell Internationale Research Maatschappij B.V. Carpet backing derived from block copolymer compositions
CN1068395C (zh) * 1993-07-23 2001-07-11 国际壳牌研究有限公司 从嵌段共聚物组合物得到的地毯背衬
WO1995017467A1 (fr) * 1993-12-20 1995-06-29 H.B. Fuller Licensing & Financing, Inc. Materiau translucide comme le verre
WO1996015189A1 (fr) * 1994-11-15 1996-05-23 The Dow Chemical Company Couches provenant de dispersions aqueuses de copolymeres en blocs contenant un bloc diene conjugue hydrogene
US5567760A (en) * 1994-11-15 1996-10-22 The Dow Chemical Company Films from aqueous dispersions of block copolymers having hydrogenated conjugated diene block
US7718721B2 (en) 2006-11-13 2010-05-18 Sabic Innovative Plastics Ip B.V. Poly(arylene ether)/polyolefin composition, method, and article
WO2018172148A1 (fr) 2017-03-22 2018-09-27 Ineos Styrolution Group Gmbh Mélange de copolymères styréniques à faible retrait
US11591462B2 (en) 2017-03-22 2023-02-28 Ineos Styrolution Group Gmbh Styrenic copolymer blend with low shrinkage

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TW209877B (fr) 1993-07-21
JPH05214208A (ja) 1993-08-24
CA2081922A1 (fr) 1993-05-05
KR930010107A (ko) 1993-06-22
AU661055B2 (en) 1995-07-13
US5278220A (en) 1994-01-11
AU2748392A (en) 1993-05-06
BR9204220A (pt) 1993-05-11

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